Method of making highly active metal oxide and metal sulfide materials

ABSTRACT

A method of making highly an active mixed transition metal oxide material has been developed. The method may include sulfiding the metal oxide material to generate metal sulfides which are used as catalyst in a conversion process such as hydroprocessing. The hydroprocessing may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

FIELD OF THE INVENTION

This invention relates to a new method of making a catalyst or catalystprecursor. More particularly this invention relates to a novel method ofmaking a mixed transition metal oxide and its use as a catalyst orcatalyst precursor such as a hydrocarbon conversion catalyst or catalystprecursor or specifically a hydroprocessing catalyst or catalystprecursor. The hydroprocessing may include hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking.

BACKGROUND

Currently there are two main drivers for refiners to invest inhydroprocessing technology. The first being environmental regulationsimposing more stringent specifications on fuels including gasoline,diesel, and even fuel oils. For example, permitted sulfur and nitrogenlevels in fuels are significantly lower than one decade ago. A seconddriving force is the quality of crude oils. More refineries are facingcrude oils containing higher concentrations of sulfur and nitrogencompounds which are difficult to process or remove by conventionalprocesses. Without new technology, refiners resort to increasing theseverity of hydrotreating processes either by increasing the reactortemperatures or decreasing space velocity through the reactor.Increasing reactor temperature has the drawback of shortening catalystlifetime. Decreasing space velocity, through increasing reactor size ordecreasing feed flow rates, has the drawback of overhauling the reactorsor significantly reducing production rates. Therefore, a highly activehydroprocessing catalyst is needed. A highly active hydroprocessingcatalyst helps the refiners meet the stringent fuel sulfur and nitrogenlimitations without significant investment in reactors and equipment andwhile maintaining production rates.

In the early 2000s, unsupported, also called “bulk”, hydrotreatingcatalysts were applied in commercial hydrotreating processes. Thesecatalysts were claimed to have several times more activity thanconventional supported NiMo or CoMo hydrotreating catalysts based on thesame loading volumes. However, to achieve the high activity, theunsupported hydrotreating catalysts often contained significantly moremetal content than the conventional supported hydrotreating catalysts.Increased metal content means the cost of the catalyst is alsoincreased. Thus, there is a need in the industry for an unsupportedcatalyst with better intrinsic activity per mass. An unsupportedcatalyst with higher intrinsic activity per mass will require less metalloading to achieve the same activity as the unsupported catalyst withless intrinsic activity at the same loading volumes.

U.S. Pat. No. 6,156,695 described a Ni—Mo—W mixed metal oxide material.The XRD pattern of this material was shown to be largely amorphous withonly two crystalline peaks, the first at d=2.53 Angstroms and the secondat d=1.70 Angstroms. U.S. Pat. No. 6,534,437 described a process forpreparing a catalyst comprising bulk catalyst particles having at leastone Group VIII non-noble metal and at least two Group VIB metals. Themetal components were stated to be at least partly in the solid stateduring the material synthesis reaction with solubility of less than 0.05mol/100 ml water at 18° C. U.S. Pat. No. 7,544,632 showed a bulkmulti-metallic catalyst composition containing quaternary ammonium,[CH₃(CH₂)_(d)N(CH₃)₃], where d is an integer from about 10 to about 40.U.S. Pat. No. 7,686,943 described a bulk metal catalyst comprising metaloxidic particles containing niobium as a Group V metal, a single GroupVIB metal, and a single Group VIII metal. U.S. Pat. No. 7,776,205described a bulk metal catalyst comprising a single Group VIB metal, aGroup VB metal, and a Group VIII metal.

U.S. Pat. No. 8,173,570 showed co-precipitation to form at least a metalcompound in solution selected from Group VIII, at least two Group VIBmetal compounds in solution, and at least one organic oxygen containingchelating ligand in solution. The organic oxygen containing ligand hasan LD50 rate larger than 700 mg/kg. U.S. Pat. No. 7,803,735 showedforming an unsupported catalyst precursor by co-precipitating at leastone of a Group VIB metal compound, at least a metal compound selectedfrom Group VIII, Group IIB, Group IIA, Group IVA, and combinationsthereof, and at least one of an organic oxygen-containing ligand.

CN 101306374 described a catalyst of at least one Group VIII metal, atleast two Group VIB metals and an organic additive. The organic additiveis selected from organic ammonium compounds with the formula ofC_(n)H_(2n+1)N(Me)₃X or (C_(n)H_(2n+1))₄NX where n=2-20 and X denotesCl, Br, or OH. The XRD provided shows peaks at d=11.30+/−1.5 Angstroms,d=4.15+/−0.5 Angstroms, d=2.60+/−0.5 Angstroms, and d=1.53+/−0.5Angstroms.

Unsupported NiZnMoW materials have been discussed in Applied CatalysisA: General 474 (2014) page 60-77. The material was synthesized in twosteps. The first step prepared layered NiZn hydroxides. The second stepprepared the NiZnMoW material via the reaction of layered NiZn hydroxideand solution containing MoO₄ ²⁻ and WO₄ ²⁻.

There is a need for new materials to meet increasing demands ofconversion processes including the need for catalysts with higherintrinsic activity per mass. Further, there is a need to synthesizethese catalysts in a manufacturing-friendly way. There is a need toproduce the catalysts and catalyst precursors without the use ofammonia, without dependence on stirring or mixing, and without the addedstep pf adjusting pH during synthesis.

SUMMARY

An embodiment involves method of making a mixed transition metal oxidematerial comprising M_(I), M_(II), M_(III), and M_(IV), where: M_(I) isoptional and if present is a metal or mixture of metals selected fromGroup IB (IUPAC Group 11), Group IIB (IUPAC Group 12), Group VIM (IUPACGroup 7), Group IIIA (IUPAC Group 13), Group IVA (IUPAC Group 14), andGroup IVB (IUPAC Group 4); M_(II) is a metal or a mixture of metalsselected from Group VIII (IUPAC Groups 8, 9, and 10); M_(III) is a metalselected from Group VIB (IUPAC Group 6); M_(IV) is a metal selected fromGroup VIB (IUPAC Group 6) which is different from M_(III); the methodcomprising: adding sources of M_(II), M_(III), M_(IV), and optionallyM_(I), to a quaternary ammonium hydroxide such as tetramethyl ammoniumhydroxide to form a slurry; reacting the slurry at a temperature fromabout 25° C. to about 200° C. for a period of time from about 30 minutesto 200 hours to generate the mixed transition metal oxide material; andrecovering the mixed transition metal oxide material. The mixedtransition metal oxide material may be sulfided to generate metalsulfides. The metal sulfides may be used as an active catalyst in aconversion process.

In one embodiment the novel mixed transition metal oxide material hasthe formula:(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)(M_(IV)^(d))_(p)O^(e) _(q)where: M_(I) is optional and if present is a metal or mixture of metalsselected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12),Group VIM (IUPAC Group 7), Group IIIA (IUPAC Group 13), Group IVA (IUPACGroup 14), and Group IVB (IUPAC Group 4); M_(II) is a metal or a mixtureof metals selected from Group VIII (IUPAC Groups 8, 9, and 10); M_(III)is a metal selected from Group VIB (IUPAC Group 6); M_(IV) is a metalselected from Group VIB (IUPAC Group 6) which is different from M_(III);a, b, c, d, and e, are the valence state of M_(I), M_(II), M_(III),M_(IV), and O; m, n, o, p, and q, are the mole ratio of M_(I), M_(II),M_(III), M_(IV), and O, wherein m/(m+n)≥0 and m/(m+n)≤1, wherein(m+n)/(o+p) is from 1/10 to 10/1, wherein o/p>0, and 0≤p/o≤100, whereinq is greater than 0, and a, b, c, d, e, m, n, o, p, and q satisfy theequation:a*m+b*n+c*o+d*p+e*q=0the material may be further characterized by an x-ray diffractionpattern comprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I_(o))  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ(°) of 55-58 has a full width at half maximumlarger than 3°.

The conversion process may be a hydrocarbon conversion process. Theconversion process may be hydroprocessing. The conversion process may behydrodenitrification, hydrodesulfurization, hydrodemetallation,hydrodesilication, hydrodearomatization, hydroisomerization,hydrotreating, hydrofining, or hydrocracking. The mixed transition metaloxide material may be present in a mixture with at least one binder andwherein the mixture comprises up to about 80 wt % binder.

Additional features and advantages of the invention will be apparentfrom the description of the invention and claims provided herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the X-ray diffraction pattern of a transition metal oxidematerial as described herein and prepared as in Examples 1 to 4.

FIG. 2 is a portion of the X-ray diffraction pattern of FIG. 1 furthershowing peak deconvolution between 2θ(°) of 45-75°.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method of making mixed transitionmetal oxide materials. The mixed transition metal oxide may compriseM_(I), M_(II), M_(III), and M_(IV), where M_(I) is optional and ifpresent is a metal or mixture of metals selected from Group IB (IUPACGroup 11), Group IIB (IUPAC Group 12), Group VIIB (IUPAC Group 7), GroupIIIA (IUPAC Group 13), Group IVA (IUPAC Group 14), and Group IVB (IUPACGroup 4); M_(II) is a metal or a mixture of metals selected from GroupVIII (IUPAC Groups 8, 9, and 10); M_(III) is a metal selected from GroupVIB (IUPAC Group 6); and M_(IV) is a metal selected from Group VIB(IUPAC Group 6) which is different from M_(III).

In one embodiment the metal oxide material has an empirical formula:(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)(M_(IV)^(d))_(p)O^(e) _(q)where: M_(I) is optional and if present is a metal or mixture of metalsselected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12),Group VIIB (IUPAC Group 7), Group IIIA (IUPAC Group 13), Group IVA(IUPAC Group 14), and Group IVB (IUPAC Group 4); M_(II) is a metal or amixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10);M_(III) is a metal selected from Group VIB (IUPAC Group 6); M_(IV) is ametal selected from Group VIB (IUPAC Group 6) which is different fromMill; a, b, c, d, and e, are the valence state of M_(I), M_(II),M_(III), M_(IV), and O; m, n, o, p, and q, are the mole ratio of M_(I),M_(II), M_(III), M_(IV), and O, wherein m/(m+n)≥0 and m/(m+n)≤1, wherein(m+n)/(o+p) is from 1/10 to 10/1, wherein o/p>0, and 0≤p/o≤100, whereinq is greater than 0, and a, b, c, d, e, m, n, o, p, and q satisfy theequation:a*m+b*n+c*o+d*p+e*q=0the material may be further characterized by an x-ray diffractionpattern comprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I_(o))  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ(°) of 55-58 has a full width at half maximumlarger than 3°. M_(I) is optional and need not be present. When M_(I) isnot present, “m” of the formula is zero. If present, M_(I) is a metal ormixture of metals selected from Group IB (IUPAC Group 11), Group IIB(IUPAC Group 12), Group VIIB (IUPAC Group 7), Group IIIA (IUPAC Group13), Group IVA (IUPAC Group 14), and Group IVB (IUPAC Group 4), in oneembodiment, M_(I) may be selected from Al, Si, Zr, Mn, Cu, Zn, and anymixture thereof. Although M_(II) is a metal or a mixture of metalsselected from Group VIII (IUPAC Groups 8, 9, and 10), in one embodimentM_(II) may be selected from Fe, Co, Ni, and any mixture thereof.Although M_(III) is a metal selected from Group VIB (IUPAC Group 6) inone embodiment, M_(III) is selected from Cr, Mo, and W. Although M_(IV)is a metal selected from Group VIB (IUPAC Group 6) which is differentfrom M_(III), in one embodiment M_(IV) is selected from Cr, Mo, and W solong as M_(IV) is different from M_(III).

Patterns presented herein were obtained using standard x-ray powderdiffraction techniques. The radiation source was a high-intensity, x-raytube operated at 45 kV and 35 mA. The diffraction pattern from thecopper K-alpha radiation was obtained by appropriate computer basedtechniques. Powder samples were pressed flat into a plate andcontinuously scanned from 3° and 70° (2θ). Interplanar spacings (d) inAngstrom units were obtained from the position of the diffraction peaksexpressed as θ, where θ is the Bragg angle as observed from digitizeddata. As will be understood by those skilled in the art thedetermination of the parameter 2θ is subject to both human andmechanical error, which in combination can impose an uncertainty ofabout ±0.4° on each reported value of 2θ. This uncertainty is alsotranslated to the reported values of the d-spacings, which arecalculated from the 2θ values. The intensity of each peak was determinedby the peak height after subtracting background. To prevent errors inpeak deconvolution, the background is taken to be linear in the rangedelimiting the broad diffraction features, 6-2 Å. To is the intensity ofthe peak at 2θ of 34.5-36.5°. I/I_(o) is the ratio of the intensity of apeak to I_(o). In terms of 100(I/I_(o)), the above designations aredefined as: vw=0-5, w=5-20, m=20-60, s=60-80, and vs=80-100. It is knownto those skilled in the art, the noise/signal ratio in XRD depends onscan conditions. Sufficient scan time is required to minimizenoise/signal ratio to measure peak intensities.

The novel mixed transition metal oxide material can be prepared byco-precipitation by adding sources of the transition metals to aquaternary ammonium hydroxide such as tetramethyl ammonium hydroxide(TMAOH) to form a slurry. A combination of more than one quaternaryammonium hydroxides may be used. Tetramethylammonium hydroxide (TMAOH)is an exemplary quaternary ammonium hydroxide to form the slurry. Otherquaternary ammonium hydroxides such as tetraethylammonium hydroxide(TEAOH), tetrapropylammonium hydroxide (TPAOH), tetrabutylammoniumhydroxide (TBAOH) and any combination thereof may be used. No additionalNH₃.H₂O or other basic solutions are necessary, and the slurry need notcontain NH₃.H₂O or other basic solutions. The slurry is then reacted ata temperature from about 25° C. to about 200° C. for a period of timefrom about 30 minutes to 200 hours to generate the mixed transitionmetal oxide material. The mixed transition metal oxide material may beconsidered a catalyst precursor which then may undergo sulfidation toform metal sulfides. Optionally, short chain alkyl quaternary ammoniumhalide compounds may be added to the quaternary ammonium hydroxide or tothe slurry. The term “metal” as used herein is meant to refer to theelement and not meant to necessarily indicate a metallic form.

The quaternary ammonium hydroxide compound may be a short-chain alkylquaternary ammonium hydroxide compound selected from compounds havingthe formula [R1 R2 R3 R4-N]OH, where R1, R2, R3 and R4 are alkyl groupshaving from 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl,pentyl, and hexyl, and R1, R2, R3 and R4 can be the same or differentfrom each other. Specific examples of short-chain alkyl quaternaryammonium hydroxide compounds include, but are not limited to, tetramethyl ammonium hydroxide, tetra ethyl ammonium hydroxide, tetra propylammonium hydroxide, tetra butyl ammonium hydroxide, tetra pentylammonium hydroxide, tri-butyl methyl ammonium hydroxide, tri-propylmethyl ammonium hydroxide, tri-ethyl methyl ammonium hydroxide,di-propyl di-methyl ammonium hydroxide, butyl tri-methyl ammoniumhydroxide, and any mixture thereof.

Sources of M_(I), if M_(I) is present, include, but are not limited to,the respective halide, sulfide, acetate, nitrate, carbonate, sulfate,oxalate, thiols, hydroxide salts, and oxides of M_(I). Specific examplesof sources of M_(I) include, but are not limited to, manganese nitrate,manganese chloride, manganese bromide, manganese sulfate, manganesecarbonate, manganese sulfide, manganese hydroxide, manganese oxide,zirconium nitrate, zirconium oxychloride, zirconium bromide, zirconiumsulfate, zirconium basic carbonate, zirconium hydroxide, zirconiumoxide, copper nitrate, copper chloride, copper bromide, copper sulfate,copper carbonate, copper acetate, copper oxalate, copper sulfide, copperhydroxide, copper oxide, zinc nitrate, zinc chloride, iron bromide, zincsulfate, zinc carbonate, zinc acetate, zinc oxalate, zinc sulfide, zinchydroxide, zinc oxide, and any mixture thereof.

Sources of M_(II) include, but are not limited to, the respectivehalide, sulfide, acetate, nitrate, carbonate, sulfate, oxalate, thiols,hydroxide salts, and oxides of M_(II). Specific examples of sources ofM_(II) include, but are not limited to, nickel chloride, nickel bromide,nickel nitrate, nickel acetate, nickel carbonate, nickel hydroxide,cobalt chloride, cobalt bromide, cobalt nitrate, cobalt acetate, cobaltcarbonate, cobalt hydroxide, cobalt sulfide, nickel chloride, cobaltoxide, nickel bromide, nickel nitrate, nickel acetate, nickel carbonate,nickel hydroxide, nickel sulfide, nickel oxide, iron acetate, ironoxalate, iron nitrate, iron chloride, iron bromide, iron sulfate, ironcarbonate, iron acetate, iron oxalate, iron sulfide, iron oxide, and anymixture thereof.

Sources of Mill include, but are not limited to, the respective oxidesof M_(III), sulfides of M_(III), halides of M_(III), molybdates,tungstates, thiolmolybdates, and thioltungstates. Specific examples ofsources of M_(III) include, but are not limited to, molybdenum trioxide,ammonium dimolybdate, ammonium thiomolybdate, ammonium heptamolybdate,sodium dimolybdate, sodium thiomolybdate, sodium heptamolybdate,potassium dimolybdate, potassium thiomolybdate, potassiumheptamolybdate, molybdenum sulfide, tungsten trioxide, tungstic acid,tungsten oxytetrachloride, tungsten hexachloride, hydrogen tungstate,ammonium ditungstate, sodium ditungstate, ammonium metatungstate,ammonium paratungstate, sodium metatungstate, sodium paratungstate, andany mixture thereof.

Sources of M_(IV) include, but are not limited to, the respective oxidesof M_(IV), sulfides of M_(IV), halides of M_(IV), molybdates,tungstates, thiolmolybdates, and thioltungstates. Specific examples ofsources of M_(IV) include, but are not limited to, molybdenum trioxide,ammonium dimolybdate, ammonium thiomolybdate, ammonium heptamolybdate,sodium dimolybdate, sodium thiomolybdate, sodium heptamolybdate,potassium dimolybdate, potassium thiomolybdate, potassiumheptamolybdate, molybdenum sulfide, tungsten trioxide, tungstic acid,tungsten oxytetrachloride, tungsten hexachloride, hydrogen tungstate,ammonium ditungstate, sodium ditungstate, ammonium metatungstate,ammonium paratungstate, sodium metatungstate, sodium paratungstate, andany mixtures thereof.

While tetramethylammonium hydroxide (TMAOH) is an exemplary quaternaryammonium hydroxide to form the slurry, other quaternary ammoniumhydroxides such as tetraethylammonium hydroxide (TEAOH),tetrapropylammonium hydroxide (TPAOH), tetrabutylammonium hydroxide(TBAOH) and any combination thereof may be used.

Optionally, a short-chain alkyl quaternary ammonium halide compound, maybe added to the quaternary ammonium hydroxide such as TMAOH or to theresulting slurry. If employed, the short-chain alkyl quaternary ammoniumhalide compound may be selected from compounds having the formula [R1 R2R3 R4-N]X, where R1, R2, R3 and R4 are alkyl groups having from 1 to 6carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl,and R1, R2, R3 and R4 can be the same or different from each other. In aspecific embodiment, X is selected from F, Cl, Br, and I. Specificexamples of short-chain alkyl quaternary ammonium halide compoundsinclude, but are not limited to, tetra methyl ammonium chloride, tetramethyl ammonium bromide, tetra ethyl ammonium chloride, tetra ethylammonium bromide, tetra propyl ammonium chloride, tetra propyl ammoniumbromide, tetra butyl ammonium chloride, tetra butyl ammonium bromide,tetra pentyl ammonium chloride, tetra pentyl ammonium bromide, tri-butylmethyl ammonia chloride, tri-butyl methyl ammonium bromide, tri-propylmethyl ammonium chloride, tri-propyl methyl ammonium bromide, tri-ethylmethyl ammonium chloride, tri-ethyl methyl ammonium bromide, di-propyldi-methyl ammonium chloride, di-propyl di-methyl ammonium bromide, butyltri-methyl ammonium chloride, butyl tri-methyl ammonium bromide, and anymixture thereof.

Although different mixed metal oxides may be prepared, in one embodimentthe mixed metal oxide material has an empirical formula:(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)(M_(IV)^(d))_(p)O^(e) _(q)where: M_(I) is optional and if present is a metal or mixture of metalsselected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12),Group VIM (IUPAC Group 7), Group IIIA (IUPAC Group 13), Group IVA (IUPACGroup 14), and Group IVB (IUPAC Group 4); M_(II) is a metal or a mixtureof metals selected from Group VIII (IUPAC Groups 8, 9, and 10); M_(III)is a metal selected from Group VIB (IUPAC Group 6); M_(IV) is a metalselected from Group VIB (IUPAC Group 6) which is different from M_(III);a, b, c, d, and e, are the valence state of M_(I), M_(II), M_(III),M_(IV), and O; m, n, o, p, and q, are the mole ratio of M_(I), M_(II),M_(III), M_(IV), and O, wherein m/(m+n)≥0 and m/(m+n)≤1, wherein(m+n)/(o+p) is from 1/10 to 10/1, wherein o/p>0, and 0≤p/o≤100, whereinq is greater than 0, and a, b, c, d, e, m, n, o, p, and q satisfy theequation:a*m+b*n+c*o+d*p+e*q=0

In this embodiment, the metal oxide material synthesized by the methodof the invention has features characterized by X-ray powder diffraction(XRD) pattern. The material may be characterized by an x-ray diffractionpattern comprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I_(o))  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ(°) of 55-58 has a full width at half maximumlarger than 3°. Additional peaks may comprise 2θ(°) 18-21, d (Å) of4.227-4.924, with 100(I/I_(o)) of vw to w; 2θ(°) 21-23, d (Å) of3.864-4.227, with 100(I/I_(o)) of m to s; 2θ(°) 30-32, d (Å) of2.795-2.976, with 100(I/I_(o)) of m to s. In one embodiment, the XRDpattern of the material comprises a peak between 2θ of 21° and 23°; apeak between 2θ of 34.5° and 36.5°; a peak between 2θ of 53° and 55°; apeak between 20 of 55° and 58° with the full width at half maximum(FWHM) larger than 3°; and a peak between 2θ of 62.8° and 63.8°.

The method of this invention provides that the mixed transition metaloxides may be prepared though co-precipitation by adding sources of thetransition metals to one or more quaternary ammonium hydroxides such asTMAOH to form a slurry. Optionally at least one short-chain alkylquaternary ammonium halide compound may be added to the one or morequaternary ammonium hydroxides such as TMAOH or to the resulting slurry.The slurry may further include protic solvents such as water andalcohols with exemplary alcohols including ethanol, isopropanol,butanol, and glycol. The slurry may be formed by adding the sources ofthe transition metals to the one or more quaternary ammonium hydroxidessuch as TMAOH in any order or in any combination. In one embodiment, thesources of M_(I), M_(II), M_(III), and M_(IV) may be in one or moresolutions prior to adding to the one or more quaternary ammoniumhydroxides such as TMAOH to form the slurry. With this method, it is notnecessary to adjust the pH of the slurry. Elimination of the need for pHadjustment simplifies manufacturing operations and eliminates the needfor additional base materials such as NH₄OH, amines, and the like, ormineral acids such as nitric acid, hydrochloric acid, sulfuric acid,hydrofluoric acid, or an organic acid such as citric acid or malic acid.Particularly advantageous is the elimination of ammonia which iscorrosive with a very pungent odor.

The slurry is reacted at a temperature in the range of about 25° C. toabout 200° C., or from about 60° C. to about 180° C., or from about 80°C. to about 150° C. in a sealed autoclave reactor or in a reactor opento ambient pressure. The sealed autoclave reactor or the reactor open toambient pressure can be optionally equipped with a stirring device tomix the slurry. In another embodiment, the sealed autoclave or thereactor open to the ambient pressure does not have a stirring device andthe reaction is conducted at a static state unless the temperature ofthe reaction mixture slurry is higher than boiling point of the slurry,causing autonomous stirring by the boiling of the reaction mixtureslurry. The success of the reaction is not tied to the stirring. Inembodiment where a reactor open to ambient pressure is employed, areflux device can be optionally attached to the reactor to avoid solventloss when the reaction temperature is close to or above the boilingtemperature of the reaction mixture slurry.

The reaction time may range from about 0.5 to about 200 h, or 0.5 h toabout 100 h, or from about 1 h to about 50 h, or from about 2 h to about24 h. Although not necessary, the slurry may be mixed continuously orintermittently during the reaction. In one embodiment, the slurry ismixed every few hours. The mixed transition metal oxide material isrecovered from the slurry. The mixed transition metal oxide material maybe considered a catalyst precursor. Sulfidation of the mixed transitionmetal oxide may be employed to generate metal sulfides which in turn areused as catalysts.

In a specific embodiment, the mixed transition metal oxide material orthe metal sulfides generated therefrom may be present in a compositionalong with a binder, where the binder may be, for example, silicas,aluminas, silica-aluminas, titanias, zirconias, natural clays, syntheticclays, and mixtures thereof. The selection of binder includes but is notlimited to, anionic and cationic clays such as hydrotalcites,pyroaurite-sjogrenite-hydrotalcites, montmorillonite and related clays,kaolin, sepiolites, silicas, aluminas such as (pseudo) boehomite,gibbsite, flash calcined gibbsite, eta-alumina, zicronica, titania,alumina coated titania, silica-alumina, silica coated alumina, aluminacoated silicas and mixtures thereof, or other materials generally knownas particle binders in order to maintain particle integrity. Thesebinders may be applied with or without peptization. The binder may beadded to the bulk mixed transition metal oxide material, or may beincorporated during synthesis. The amount of binder may range from about1 to about 80 wt % of the finished composition, or from about 1 to about30 wt % of the finished composition, or from about 5 to about 26 wt % ofthe finished composition. The binder may be chemically bound to themixed transition metal oxide material or metal sulfides, or the bindermay be present in a physical mixture with the novel mixed transitionmetal oxide material or resulting metal sulfides. The mixed transitionmetal oxide material or metal sulfides may be extruded or pelletizedwith or without a binder.

At least a portion of the mixed transition metal oxide material, with orwithout a binder, or before or after inclusion of a binder, can besulfided in situ in an application or pre-sulfided to form metalsulfides which in turn are used as catalysts in an application. Thesulfidation may be conducted under a variety of sulfidation conditionssuch as through contact of the mixed transition metal oxide materialwith a sulfur containing stream or feedstream as well as the use of agaseous mixture of H₂S/H₂. The sulfidation of the mixed transition metaloxide material is performed at elevated temperatures, typically rangingfrom 50 to 600° C., or from 150 to 500° C., or from 250 to 450° C. Thesulfiding step can take place at a location remote from other synthesissteps, remote from the location of the application where the mixedtransition metal oxide material will be used, or remote from both thelocation of synthesis and remote from location of use. The materialsresulting from the sulfiding step are referred to as metal sulfideswhich can be used as catalysts in conversion processes.

As discussed, at least a portion of the mixed transition metal oxidematerial of this invention can be sulfided and the resulting metalsulfides used as catalysts in conversion processes such as hydrocarbonconversion processes. Hydroprocessing is one class of hydrocarbonconversion processes in which the mixed transition metal oxide materialis useful as a catalyst. Examples of specific hydroprocessing processesare well known in the art and include hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking. In one embodiment a conversion process comprisescontacting the mixed transition metal oxide material with a sulfidingagent to generate metal sulfides which are contacted with a feed streamat conversion conditions to generate at least one product.

The operating conditions of the hydroprocessing processes listed abovetypically include reaction pressures from about 2.5 MPa to about 17.2MPa, or in the range of about 5.5 to about 17.2 MPa, with reactiontemperatures in the range of about 245° C. to about 440° C., or in therange of about 285° C. to about 425° C. Contact time for the feed andthe active catalyst, referred to as liquid hourly space velocities(LHSV), should be in the range of about 0.1 h⁻¹ to about 10 or about0.25 to about 8.0 Specific subsets of these ranges may be employeddepending upon the feedstock being used. For example, when hydrotreatinga typical diesel feedstock, operating conditions may include from about3.5 MPa to about 8.6 MPa, from about 315° C. to about 410° C., fromabout 0.25 to about 5 and from about 84 Nm³ H₂/m³ to about 850 Nm³ H₂/m³feed. Other feedstocks may include gasoline, naphtha, kerosene, gasoils, distillates, and reformate.

Examples are provided below to describe the invention more completely.These examples are only by way of illustration and should not beinterpreted as a limitation of the broad scope of the invention, whichis set forth in the claims.

Example 1

16.01 g of TMAOH was set to stir in a beaker. 0.86 g of zinc acetatedissolved in 5 g deionized water was added to the TMAOH followed by theaddition of a solution containing 1.62 g of ammonium heptamolybdate,2.93 g of ammonium metatungstate, 4.54 g nickel nitrate, and 49 gdeionized water. The resulting slurry was stirred and transferred to a45 ml Parr reactor. The slurry was then digested at 150° C. for 17 hoursin a tumbled oven. After the completion of the synthesis, theprecipitated mixed transition metal oxide was recovered and washed bycentrifugation. Then the mixed transition metal oxide was dried in airand sulfided in a H₂S/H₂ atmosphere to form metal sulfides. The metalsulfides were tested as a catalyst for conversion of 2-methylnaphthalene in H₂ to hydrogenated products and showed 74 wt. %conversion at 300° C. The mixed transition metal oxide, beforesulfidation, was analyzed by x-ray powder diffraction and found to havean x-ray diffraction pattern comprising the peaks in Table A.

Example 2

16.01 g of TMAOH was set to stir in a beaker. 0.86 g of zinc acetatedissolved in 5 g deionized water was added to the TMAOH followed by theaddition of a solution containing 1.62 g of ammonium heptamolybdate,2.93 g of ammonium metatungstate, 4.54 g nickel nitrate, and 49 gdeionized water. The resulting slurry was stirred and transferred to a45 ml Parr reactor. The slurry was then digested at 100° C. for 18.5hours in a static oven. After the completion of the synthesis, theprecipitated mixed transition metal oxide was recovered and washed bycentrifugation. Then the mixed transition metal oxide was dried in airand sulfided in a H₂S/H₂ atmosphere to form metal sulfides. The metalsulfides were tested as a catalyst for conversion of 2-methylnaphthalene in H₂ to hydrogenated products and showed 79 wt. %conversion at 300° C. The mixed transition metal oxide, beforesulfidation, was analyzed by by x-ray powder diffraction and found tohave an x-ray diffraction pattern comprising the peaks in Table A.

Example 3

16.01 g of TMAOH was set to stir in a beaker. 0.86 g of zinc acetate and3.92 g nickel nitrate dissolved in 34.49 g deionized water was added tothe TMAOH followed by the addition of a solution containing 1.63 g ofammonium heptamolybdate, 2.96 g of ammonium metatungstate, and 20 gdeionized water. The resulting slurry was stirred and transferred to a45 ml Parr reactor. The slurry was then digested at 175° C. for 17 hoursin a tumbled oven. After the completion of the synthesis, theprecipitated mixed transition metal oxide was recovered and washed bycentrifugation. Then the mixed transition metal oxide was dried in airand sulfided in a H₂S/H₂ atmosphere to form metal sulfides. The metalsulfides were tested as a catalyst for conversion of 2-methylnaphthalene in H₂ to hydrogenated products and showed 77 wt. %conversion at 300° C. The mixed transition metal oxide, beforesulfidation, was analyzed by by x-ray powder diffraction and found tohave an x-ray diffraction pattern comprising the peaks in Table A.

Example 4

16.01 g of TMAOH was set to stir in a beaker. 0.86 g of zinc acetate and3.92 g nickel nitrate dissolved in 34.49 g deionized water was added tothe TMAOH followed by the addition of a solution containing 1.63 g ofammonium heptamolybdate, 2.96 g of ammonium metatungstate, and 20 gdeionized water. The resulting slurry was stirred and transferred to a45 ml Parr reactor. The slurry was then digested at 100° C. for 18.5hours in a tumbled oven After the completion of the synthesis, theprecipitated mixed transition metal oxide was recovered and washed bycentrifugation. Then the mixed transition metal oxide was dried in airand sulfided in a H₂S/H₂ atmosphere to form metal sulfides. The metalsulfides were tested as a catalyst for conversion of 2-methylnaphthalene in H₂ to hydrogenated products and showed 74 wt. %conversion at 300° C. The mixed transition metal oxide, beforesulfidation, was analyzed by by x-ray powder diffraction and found tohave an x-ray diffraction pattern comprising the peaks in Table A.

Embodiments

While the following is described in conjunction with specificembodiments, it will be understood that this description is intended toillustrate and not limit the scope of the preceding description and theappended claims.

A first embodiment is a method of making a mixed transition metal oxidematerial comprising M_(I), M_(II), M_(III), and M_(IV), where:

-   -   M_(I) is optional and if present is a metal or mixture of metals        selected from Group D3 (IUPAC Group 11), Group IIB (IUPAC Group        12), Group VIIB (IUPAC Group 7), Group IIIA (IUPAC Group 13),        Group IVA (IUPAC Group 14), and Group IVB (IUPAC Group 4);    -   M_(II) is a metal or a mixture of metals selected from Group        VIII (IUPAC Groups 8, 9, and 10);    -   M_(III) is a metal selected from Group VIB (IUPAC Group 6);    -   M_(IV) is a metal selected from Group VIB (IUPAC Group 6) which        is different from M_(III);    -   the method comprising:    -   (a) adding sources of M_(II), M_(III), M_(IV), and optionally        M_(I), to at least one quaternary ammonium hydroxide to form a        slurry;    -   (b) reacting the slurry at a temperature from about 25° C. to        about 200° C. for a period from about 30 minutes to 200 hours to        generate the mixed transition metal oxide material; and    -   (c) recovering the mixed transition metal oxide material.

The first embodiment wherein the mixed transition metal oxide materialhas the formula:(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)(M_(IV)^(d))_(p)O^(e) _(q)where:

-   -   M_(I) is optional and if present is a metal or mixture of metals        selected from Group D3 (IUPAC Group 11), Group IIB (IUPAC Group        12), Group VIIB (IUPAC Group 7), Group IIIA (IUPAC Group 13),        Group IVA (IUPAC Group 14), and Group IVB (IUPAC Group 4);    -   M_(II) is a metal or a mixture of metals selected from Group        VIII (IUPAC Groups 8, 9, and 10);    -   M_(III) is a metal selected from Group VIB (IUPAC Group 6);    -   M_(IV) is a metal selected from Group VIB (IUPAC Group 6) which        is different from M_(III);    -   a, b, c, d, and e are the valence state of M_(I), M_(II),        M_(III), M_(IV), and O;    -   m, n, o, p, and q are the mole ratio of M_(I), M_(II), M_(III),        M_(IV), and O, wherein m/(m+n)≥0 and m/(m+n)≤1, wherein        (m+n)/(o+p) is from 1/10 to 10/1, wherein o/p>0, and 0≤p/o≤100,        wherein q is greater than 0, and a, b, c, d, e, m, n, o, p, and        q satisfy the equation:        a*m+b*n+c*o+d*p+e*q=0        the material further characterized by an x-ray diffraction        pattern comprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I_(o))  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ(°) of 55-58 has a full width at half maximumlarger than 3°.

The first embodiment wherein M_(I), if present, is Si, Zr, Mn, Cu, Zn,or any mixture thereof. The first embodiment wherein M_(II) is Fe, Co,Ni, or any mixture thereof. The first embodiment wherein M_(III) is Cr,Mo, or W. The first embodiment wherein M_(IV) is Cr, Mo, or W and isdifferent from M_(III). The first embodiment further comprisingsulfiding at least a portion of the recovered mixed transition metaloxide material to form metal sulfides. The first embodiment wherein thequaternary ammonium hydroxide is selected from tetramethylammoniumhydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH),tetrapropylammonium hydroxide (TPAOH), tetrabutylammonium hydroxide(TBAOH) and any combination thereof. The first embodiment furthercomprising adding a binder to the reaction mixture or to the recoveredmixed transition metal oxide material wherein the binder is selectedfrom aluminas, silicas, alumina-silicas, titanias, zirconias, naturalclays, synthetic clays, and mixtures thereof. The first embodimentwherein the reacting is conducted under atmospheric pressure orautogenous pressure. The first embodiment further comprising mixing theslurry. The first embodiment wherein the temperature is varied duringthe reacting. The first embodiment further comprising adding, to the atleast one quaternary ammonium hydroxide or to the slurry, at least oneshort-chain alkyl quaternary ammonium halide compound having the formula[R1 R2 R3 R4-N]X, where R1, R2, R3 and R4 are alkyl groups having 1 to 6carbon atoms, and R1, R2, R3 and R4 can be the same or different.

A second embodiment of method of making metal sulfides from a mixedtransition metal oxide material comprising M_(I), M_(II), M_(III), andM_(IV), where:

-   -   M_(I) is optional and if present is a metal or mixture of metals        selected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group        12), Group VIIB (IUPAC Group 7), Group IIIA (IUPAC Group 13),        Group IVA (IUPAC Group 14), and Group IVB (IUPAC Group 4);    -   M_(II) is a metal or a mixture of metals selected from Group        VIII (IUPAC Groups 8, 9, and 10);    -   M_(III) is a metal selected from Group VIB (IUPAC Group 6);    -   M_(IV) is a metal selected from Group VIB (IUPAC Group 6) which        is different from M_(III);    -   the method comprising:    -   (d) adding sources of M_(II), M_(III), M_(IV), and optionally        M_(I), to at least one quaternary ammonium hydroxide to form a        slurry;    -   (e) reacting the slurry at a temperature from about 25° C. to        about 200° C. for a period of time from about 30 minutes to 200        hours to generate the mixed transition metal oxide material;    -   (f) recovering the mixed transition metal oxide material; and    -   (g) sulfiding at least a portion of the mixed transition metal        oxide material to form metal sulfides.

The second embodiment wherein M_(I), when present, is Si, Zr, Mn, Cu,Zn, or any mixture thereof; M_(II) is Fe, Co, Ni, or any mixturethereof; M_(III) is Cr, Mo, or W; and M_(IV) is Cr, Mo, or W and isdifferent from M_(III). The second embodiment wherein the quaternaryammonium hydroxide is tetramethylammonium hydroxide (TMAOH), ortetraethylammonium hydroxide (TEAOH), tetrapropylammonium hydroxide(TPAOH), tetrabutylammonium hydroxide (TBAOH) and any mixtures thereof.The second embodiment further comprising adding a binder to the reactionmixture or to the recovered mixed transition metal oxide materialwherein the binder is selected from aluminas, silicas, alumina-silicas,titanias, zirconias, natural clays, synthetic clays, and mixturesthereof. The second embodiment further comprising mixing the slurry. Thesecond embodiment wherein the temperature is varied during the reacting.The second embodiment further comprising adding, to the at least onequaternary ammonium hydroxide or to the slurry, at least one short-chainalkyl quaternary ammonium halide compound having the formula [R1 R2 R3R4-N]X, where R1, R2, R3 and R4 are alkyl groups having 1 to 6 carbonatoms, and R1, R2, R3 and R4 can be the same or different.

Without further elaboration, it is believed that using the precedingdescription that one skilled in the art can utilize the presentinvention to its fullest extent and easily ascertain the essentialcharacteristics of this invention, without departing from the spirit andscope thereof, to make various changes and modifications of theinvention and to adapt it to various usages and conditions. Thepreceding preferred specific embodiments are, therefore, to be construedas merely illustrative, and not limiting the remainder of the disclosurein any way whatsoever, and that it is intended to cover variousmodifications and equivalent arrangements included within the scope ofthe appended claims. In the foregoing, all temperatures are set forth indegrees Celsius and, all parts and percentages are by weight, unlessotherwise indicated.

The invention claimed is:
 1. A method of making a mixed transition metaloxide material comprising M_(I), M_(II), M_(III), and M_(IV), where:M_(I) is optional and if present is a metal or mixture of metalsselected from Group IB (IUPAC Group 11), Group IIB (IUPAC Group 12),Group VIIB (IUPAC Group 7), Group IIIA (IUPAC Group 13), Group IVA(IUPAC Group 14), and Group IVB (IUPAC Group 4); M_(II) is a metal or amixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10);M_(III) is a metal selected from Group VIB (IUPAC Group 6); M_(IV) is ametal selected from Group VIB (IUPAC Group 6) which is different fromM_(III), the material further characterized by an x-ray diffractionpattern comprising the peaks in Table A: TABLE A 2θ (°) d (Å)100(I/I_(o))  8-14  6.320-11.043 vw 34.5-36.5 2.460-2.598 vs 53-551.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.5 1.485-1.576 vw62.8-63.8 1.458-1.478 m

wherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°; the method comprising: (a) adding sources of M_(II),M_(III), M_(IV), and optionally M_(I), to at least one quaternaryammonium hydroxide to form a slurry; (b) reacting the slurry at atemperature from about 25° C. to about 200° C. for a period from about30 minutes to 200 hours to generate the mixed transition metal oxidematerial; and (c) recovering the mixed transition metal oxide material.2. The method of claim 1 wherein the mixed transition metal oxidematerial has the formula:(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)(M_(IV)^(d))_(p)O^(e) _(q) where: M_(I) is optional and if present is a metalor mixture of metals selected from Group IB (IUPAC Group 11), Group IIB(IUPAC Group 12), Group VIIB (IUPAC Group 7), Group IIIA (IUPAC Group13), Group IVA (IUPAC Group 14), and Group IVB (IUPAC Group 4); M_(II)is a metal or a mixture of metals selected from Group VIII (IUPAC Groups8, 9, and 10); M_(III) is a metal selected from Group VIB (IUPAC Group6); M_(IV) is a metal selected from Group VIB (IUPAC Group 6) which isdifferent from M_(III); a, b, c, d, and e are the valence state ofM_(I), M_(II), M_(III), M_(IV), and O; m, n, o, p, and q are the moleratio of M_(I), M_(II), M_(III), M_(IV), and O, wherein m/(m+n)≥0 andm/(m+n)≤1, wherein (m+n)/(o+p) is from 1/10 to 10/1, wherein o/p>0, and0≤p/o≤100, wherein q is greater than 0, and a, b, c, d, e, m, n, o, p,and q satisfy the equation:a*m+b*n+c*o+d*p+e*q=0.
 3. The method of claim 1 wherein M_(I), ifpresent, is Si, Zr, Mn, Cu, Zn, or any mixture thereof.
 4. The method ofclaim 1 wherein M_(II) is Fe, Co, Ni, or any mixture thereof.
 5. Themethod of claim 1 wherein M_(III) is Cr, Mo, or W.
 6. The method ofclaim 1 wherein M_(IV) is Cr, Mo, or W and is different from M_(III). 7.The method of claim 1 further comprising sulfiding at least a portion ofthe recovered mixed transition metal oxide material to form metalsulfides.
 8. The method of claim 1 wherein the quaternary ammoniumhydroxide is selected from tetramethylammonium hydroxide (TMAOH),tetraethylammonium hydroxide (TEAOH), tetrapropylammonium hydroxide(TPAOH), tetrabutylammonium hydroxide (TBAOH) and any combinationthereof.
 9. The method of claim 1 further comprising adding a binder tothe reaction mixture or to the recovered mixed transition metal oxidematerial wherein the binder is selected from aluminas, silicas,alumina-silicas, titanias, zirconias, natural clays, synthetic clays,and mixtures thereof.
 10. The method of claim 1 wherein the reacting isconducted under atmospheric pressure or autogenous pressure.
 11. Themethod of claim 1 further comprising mixing the slurry.
 12. The methodof claim 1 wherein the temperature is varied during the reacting. 13.The method of claim 1 further comprising adding, to the at least onequaternary ammonium hydroxide or to the slurry, at least one short-chainalkyl quaternary ammonium halide compound having the formula [R1 R2 R3R4-N]X, where R1, R2, R3 and R4 are alkyl groups having 1 to 6 carbonatoms, and R1, R2, R3 and R4 can be the same or different.